CN102912133A - Method for classifying and purifying heavy metals in electroplating sludge - Google Patents
Method for classifying and purifying heavy metals in electroplating sludge Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 65
- 238000009713 electroplating Methods 0.000 title claims abstract description 43
- 239000010802 sludge Substances 0.000 title claims abstract description 42
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 156
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 77
- 239000011701 zinc Substances 0.000 claims abstract description 77
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 75
- 239000011651 chromium Substances 0.000 claims abstract description 53
- 238000000605 extraction Methods 0.000 claims abstract description 51
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 claims abstract description 42
- 239000010949 copper Substances 0.000 claims abstract description 42
- 238000002386 leaching Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 70
- 239000002893 slag Substances 0.000 claims description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 45
- 238000000746 purification Methods 0.000 claims description 42
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 38
- 238000001556 precipitation Methods 0.000 claims description 32
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- WYMDDFRYORANCC-UHFFFAOYSA-N 2-[[3-[bis(carboxymethyl)amino]-2-hydroxypropyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)CN(CC(O)=O)CC(O)=O WYMDDFRYORANCC-UHFFFAOYSA-N 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- 239000012141 concentrate Substances 0.000 claims description 7
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 7
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- QFSKIUZTIHBWFR-UHFFFAOYSA-N chromium;hydrate Chemical compound O.[Cr] QFSKIUZTIHBWFR-UHFFFAOYSA-N 0.000 claims 1
- 238000005363 electrowinning Methods 0.000 claims 1
- 239000000284 extract Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 229910052979 sodium sulfide Inorganic materials 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 19
- 238000011084 recovery Methods 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000005554 pickling Methods 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 abstract 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 235000010265 sodium sulphite Nutrition 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 238000005987 sulfurization reaction Methods 0.000 description 9
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 7
- 239000002956 ash Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for classifying and purifying heavy metals in electroplating sludge. The method includes steps of S1, performing acid pickling for the electroplating sludge; S2, performing vulcanization to settle copper; S3, performing extraction and separation to obtain zinc; S4, concentrating chromium; and S5, recycling nickel. The method for classifying and purifying the heavy metals has the advantages that a process is simple and feasible, the operating cost and energy consumption are low, and large-scale industrial production can be realized; physical and chemical properties of the electroplating sludge fed into leaching agents are changed, the most suitable condition is provided for optimally separating each metal from the electroplating sludge, the copper, the zinc, the chromium and the nickel are sequentially separated from the electroplating sludge, and accordingly the recovery rates of the metals are high; and the heavy metals are recycled, waste residues generated in a treatment process are few, detoxication is thorough, environmental pollution is prevented, the method is good in environmental protection and can bring economical benefit, and the like.
Description
Technical field
The present invention relates to the chemical technology field of electric plating sludge resource, particularly the grading purification method of heavy metal in a kind of electroplating sludge.
Background technology
Electroplating sludge mainly comes from the solid waste that the various electroplating effluents of industrial Electroplate Factory and cell liquid produce after by chemical treatment, its main component is chromium, copper, zinc, nickel, iron, aluminium, magnesium, calcium, silicon, sulphur, cyanogen etc., because containing a large amount of poisonous and hazardous heavy metals, belong to controlled poisonous industrial waste.Along with the development of modernization industry, the quantity discharged of electroplating sludge presents the year by year situation of rapid growth, produces extensive electroplating sludge.If do not deal carefully with, eliminate objectionable impurities, will produce greatly harm to human body and environment.
Metallic element in the electroplating sludge usually with the content of copper, zinc, chromium and nickel for the highest, it is a kind of secondary renewable resources, wherein the own warp of the content of some metal is considerably beyond the grade in metallic ore, all more than 10%, can be regarded as a kind of in addition recycling of resource of preciousness such as the content of metallic element common in the electroplating industries such as copper, nickel, chromium fully.To the resource utilization of electroplating sludge, innoxious be the emphasis of environmental scientific research always, if can realize its recycling, not only solved environmental problem, brought again economic benefit.
In recent years, done a lot of research aspect the recycling of people's heavy metal in electroplating sludge, also can see many method of resource about heavy metal in the electroplating sludge, but the independent separation and purification of each heavy metal species seldom has report, and loaded down with trivial details to the heavy metal purification step in the electroplating sludge, often need secondary separation, increased virtually cost, Chinese patent (application number: 200910184773.9) relate to and reclaim copper in the electroplating sludge for example, nickel, chromium, zinc, the method of iron, the separation and concentration stage obtains in sulfuration is copper, nickel, the sulfide of zinc, the vulcanized slag that obtains also needs further to process, and leaches such as hot pressing, and copper is leached, obtain scum, follow-uply copper is extracted, this moment, extraction can obtain again the extraction liquid of several metal mixed, still need process separation again.
There are the following problems for prior art:
1, running cost is higher, and energy consumption is many;
2, the mixing slag of several metals still needs to continue to separate, and processing cost can rise thereupon;
3, waste residue is more in the treating processes, and it is not thorough to detoxify, and the feature of environmental protection is good not;
Summary of the invention
In order to overcome the defective of prior art, the invention discloses the grading purification method of heavy metal in a kind of electroplating sludge, this grading purification method flow is simple, and running cost is lower, and energy consumption is few, can go out heavy metal by grading purification from electroplating sludge; The advantages such as and realized the resource utilization of heavy metal, waste residue is few in the treating processes, and it is thorough to detoxify can be to environment, and the feature of environmental protection is good and can bring economic benefit.
The invention discloses following technical scheme:
The grading purification method of heavy metal comprises the steps: in a kind of electroplating sludge
S1: the acidleach of electroplating sludge is processed;
S2: the heavy copper of sulfuration;
S3: extracting and separating zinc;
S4: enrichment chromium;
S5: reclaim nickel.
Preferably, described grading purification method, step S1 further comprises: the electroplating sludge of cupric, zinc, chromium, nickel is placed in the reactor, as reaction medium, adds hydrogen peroxide with sulfuric acid, react complete after, filter press obtains filter residue and acid leaching liquor.
Preferably, described grading purification method, the addition of its hydrogen peroxide is 5-25Kg/t.
Preferably, described grading purification method, the pH value of its reaction system is 1.0-5.0.
Preferably, described grading purification method, step S2 further comprises: leach liquor is heated to 20-100 ℃, and then slowly adds sodium sulphite in leach liquor, reacted 1-2 hour, filter, can obtain vulcanizing copper ashes and zinc, chromium, nickel solution.
Preferably, described grading purification method, its sulfuration copper ashes is further purified and obtains copper sulfide concentrate.
Preferably, described grading purification method, the add-on of its sodium sulphite be chemical mol ratio 1-1.5 doubly.
Preferably, described grading purification method, step S3 further comprises: use the extraction agent extracting zinc, stay in the organic phase through the zinc of extraction.
Preferably, described grading purification method is stripped to load organic phases with sulfuric acid, obtains the high zinc of purity, and described sulfuric acid concentration is 120-150g/L, compares O/A=1:1-5:1; Shaking does time is 3-5 minute.
Preferably, described grading purification method, its extraction agent is selected from one or more in DPTA, EDTA, phosphoric acid four butyl esters or the di-(2-ethylhexyl)phosphoric acid ester.
Preferably, described grading purification method, its extractant concentration is 20-50%, compares O/A=1:1-5:1, extraction time is 3-5 minute.
Preferably, described grading purification method, step S4 further comprises:
Add calcium carbonate the solution that vulcanizes after heavy copper and extraction dezincify is carried out one section dechromisation, chromium changes into precipitation, and part of nickel changes into the subcarbonate precipitation, filters, and gets dechromisation slag and the first solution, adopts sour water washing dechromisation slag to get the second solution.
Preferably, described grading purification method adds calcium carbonate in the mixed solution of the first solution and the second solution, filters, and gets dechromisation slag and the 3rd solution, adopts sour water washing dechromisation slag to get the 4th solution.
Preferably, described grading purification method, step S5 further comprises:
Be that three solution and the four molten mixed solution of precipitation agent after to dechromisation carries out the nickel enrichment with soda ash, obtain the nickelous carbonate precipitation, filtering separation is dissolved with sulphuric acid soln the nickel slag, by electrodeposition process metallic nickel is reclaimed.
Preferably, described grading purification method, precipitation temperature is 85-90 ℃, and the reaction times is 2-4 hour, and endpoint pH is 7.8-8.0.
Compared with prior art, beneficial effect of the present invention is as follows:
1, the grading purification method flow grading purification method flow of heavy metal is simple in the electroplating sludge of the present invention, and running cost is lower, and energy consumption is few, can realize large-scale industrial production;
2, the grading purification method of heavy metal changes the physico-chemical property that electroplating sludge advances leach liquor in the electroplating sludge of the present invention, for the optimization of every kind of metal from optimum condition is provided, copper, zinc, chromium, nickel are separated successively, thereby so that the rate of recovery of these metals is higher; Compare the method for once separating simultaneously a few heavy metal species mixing slags and have more actual value, the mixing slag of several metals still needs to continue to separate, and processing cost can rise thereupon;
3, the grading purification method of heavy metal has realized the resource utilization of heavy metal in the electroplating sludge of the present invention, and the advantage such as waste residue is few in the treating processes, and it is thorough to detoxify can be to environment, and the feature of environmental protection is good and can bring economic benefit;
4, adopt the scheme of two sections dechromisations in the electroplating sludge of the present invention in the enrichment process of chromium nickel, overcome the hydrolytic precipitation method and from the chromium nickel solution, optionally precipitated chromic shortcoming, because the pH value that chromic oxyhydroxide precipitates fully is lower than the oxyhydroxide initial precipitation pH value of nickel, nickel with subsalt (3NiSO in chromic precipitation process
44Ni (OH)
2) separated out (the pH value of its formation is 5.10) simultaneously, be lower than the chromic pH value (5.62) that precipitates fully.This scheme is effectively avoided and the loss of nickel when having reduced hydrolytic precipitation chromium.
Description of drawings
Fig. 1 is the schematic flow sheet of specific embodiment of the invention grading purification method;
Fig. 2 is the structural representation of specific embodiment of the invention grading purification method application example flow process.
Embodiment:
Such as Fig. 1 and Fig. 2, operation steps of the present invention has: S1: the acidleach of electroplating sludge is processed; S2: the heavy copper of sulfuration; S3: extracting and separating zinc; S4: enrichment chromium; S5: reclaim nickel.
Embodiment 1
1, the acidleach of electroplating sludge is processed: electroplating sludge is pumped in the reactor, add sulfuric acid, the pH of stirring reaction system is 1.0, adds hydrogen peroxide according to 5Kg/t mud, and the rear slurry that reacts completely send press filtration to separate, and obtains metal acid leaching solution and body refuse.
2, the heavy copper of sulfuration: leach liquor is heated to 20 ℃, keeping pH is 1.0, directly in stirred reactor, slowly add sodium sulphite, the add-on of sodium sulphite is 1.1 times of chemical molar weight, reaction 1h, the copper of this moment has been separated with zinc, chromium, nickel, can obtain vulcanizing copper ashes and zinc, chromium, nickel solution through filtering, be further purified and obtain copper sulfide concentrate, the sulfide precipitation rate of copper reaches 80%.
3, extracting and separating zinc: add the zinc extraction agent in zinc, chromium, the nickel leach liquor to containing, it is 20% extracting zinc that described zinc extraction agent adopts one or more extraction agents of DPTA, EDTA, phosphoric acid four butyl esters, di-(2-ethylhexyl)phosphoric acid ester to be mixed with by a certain percentage concentration, compare O/A and be defined as 1:1, extraction time is 4min, through the one-level extraction, the percentage extraction of zinc reaches 91.5%.Zinc through the one-level extraction is stayed in the organic phase, with sulfuric acid load organic phases is stripped, and the sulfuric acid concentration of adding is 120g/L, compares O/A=1:1, and shaking does time is 4min, then obtains the high zinc of purity, realizes the separation of zinc.
4, enrichment chromium: carry out one section dechromisation adding calcium carbonate to the solution that vulcanizes after heavy copper and extraction dezincify, the add-on of calcium carbonate is 0.4 times of chemical mol ratio, and the Cr precipitation reaches 70%, and the deposition rate of nickel is 10%, filters, and obtains dechromisation slag and the first solution.With sour water washing dechromisation slag, the nickel in the slag more than 60% is washed out again, and the chromium more than 98% is left in the slag simultaneously, and the most of vitriol for being adsorbed of the nickel in the leached mud obtains the second solution.Carry out two sections degree of depth dechromisations on the basis of one section preliminary dechromisation, in the mixed solution of the first solution and the second solution, add calcium carbonate, filter, get dechromisation slag and the 3rd solution, adopt sour water washing dechromisation slag to get the 4th solution, two sections dechromisation slags return the leaching operation, and the dechromisation rate can reach more than 90%, and the Ni rate of recovery can reach more than 92%.
5, the recovery of nickel: add calcined soda for industry (Na in the liquid behind the dechromisation
2CO
3) carrying out the enrichment of nickel, the control precipitation temperature is 85 ℃, and the reaction times is 2 h, and endpoint pH is 7.8 to obtain the nickelous carbonate precipitation, by electrodeposition process nickel is reclaimed, and the comprehensive recovery of nickel reaches more than 94%.
Embodiment 2
1, the acidleach of electroplating sludge is processed: electroplating sludge is pumped in the reactor, add sulfuric acid, the pH of stirring reaction system is 2.0, adds hydrogen peroxide according to 10Kg/t mud, and the rear slurry that reacts completely send press filtration to separate, and obtains metal acid leaching solution and body refuse.
2, the heavy copper of sulfuration: leach liquor is heated to 40 ℃, keeping pH is 2.0, directly in stirred reactor, slowly add sodium sulphite, the add-on of sodium sulphite is 1.2 times of chemical mol ratio, reaction 1h, the copper of this moment has been separated with zinc, chromium, nickel, can obtain vulcanizing copper ashes and zinc, chromium, nickel solution through filtering, be further purified and obtain copper sulfide concentrate, the sulfide precipitation rate of copper reaches 82.1%.
3, extracting and separating zinc: add the zinc extraction agent in zinc, chromium, the nickel leach liquor to containing, it is 30% extracting zinc that described zinc extraction agent adopts one or more extraction agents of DPTA, EDTA, phosphoric acid four butyl esters, di-(2-ethylhexyl)phosphoric acid ester to be mixed with by a certain percentage concentration, compare O/A and be defined as 2:1, extraction time is 4min, through the one-level extraction, the percentage extraction of zinc reaches 94.5%.Zinc through the one-level extraction is stayed in the organic phase, with sulfuric acid load organic phases is stripped, and the sulfuric acid concentration of adding is 130g/L, compares O/A=2:1, and shaking does time is 4min, then obtains the high zinc of purity, realizes the separation of zinc.
4, enrichment chromium: carry out one section dechromisation adding calcium carbonate to the solution that vulcanizes after heavy copper and extraction dezincify, the add-on of calcium carbonate is 0.5 times of chemical mol ratio, and the Cr precipitation reaches 98%, and the deposition rate of nickel is 12%, filters, and obtains dechromisation slag and the first solution.With sour water washing dechromisation slag, the nickel in the slag more than 60% is washed out again, and the chromium more than 98% is left in the slag simultaneously, and the most of vitriol for being adsorbed of the nickel in the leached mud obtains the second solution.Carry out two sections degree of depth dechromisations on the basis of one section preliminary dechromisation, in the mixed solution of the first solution and the second solution, add calcium carbonate, filter, get dechromisation slag and the 3rd solution, adopt sour water washing dechromisation slag to get the 4th solution, two sections dechromisation slags return the leaching operation, and the dechromisation rate can reach more than 93%, and the Ni rate of recovery can reach more than 95%.
5, the recovery of nickel: add calcined soda for industry (Na in the liquid behind the dechromisation
2CO
3) carrying out the enrichment of nickel, the control precipitation temperature is 90 ℃, and the reaction times is 2.5 h, and endpoint pH is 8.0 to obtain the nickelous carbonate precipitation, by electrodeposition process nickel is reclaimed, and the comprehensive recovery of nickel reaches more than 94%.
Embodiment 3
1, the acidleach of electroplating sludge is processed: electroplating sludge is pumped in the reactor, add sulfuric acid, the pH of stirring reaction system is 3.0, adds hydrogen peroxide according to 10Kg/t mud, and the rear slurry that reacts completely send press filtration to separate, and obtains metal acid leaching solution and body refuse.
2, the heavy copper of sulfuration: leach liquor is heated to 60 ℃, keeping pH is 3.0, directly in stirred reactor, slowly add sodium sulphite, the add-on of sodium sulphite is 1.3 times of chemical mol ratio, reaction 1h, the copper of this moment has been separated with zinc, chromium, nickel, can obtain vulcanizing copper ashes and zinc, chromium, nickel solution through filtering, be further purified and obtain copper sulfide concentrate, the sulfide precipitation rate of copper reaches 92.1%.
3, extracting and separating zinc: add the zinc extraction agent in zinc, chromium, the nickel leach liquor to containing, it is 40% extracting zinc that described zinc extraction agent adopts one or more extraction agents of DPTA, EDTA, phosphoric acid four butyl esters, di-(2-ethylhexyl)phosphoric acid ester to be mixed with by a certain percentage concentration, compare O/A and be defined as 3:1, extraction time is 4min, through the one-level extraction, the percentage extraction of zinc reaches 97.1%.Zinc through the one-level extraction is stayed in the organic phase, with sulfuric acid load organic phases is stripped, and the sulfuric acid concentration of adding is 140g/L, compares O/A=3:1, and shaking does time is 4min, then obtains the high zinc of purity, realizes the separation of zinc.
4, enrichment chromium: carry out one section dechromisation adding calcium carbonate to the solution that vulcanizes after heavy copper and extraction dezincify, the add-on of calcium carbonate is 0.6 times of chemical mol ratio, and the Cr precipitation reaches 95%, and the deposition rate of nickel is 30%, filters, and obtains dechromisation slag and the first solution.With sour water washing dechromisation slag, the nickel in the slag more than 60% is washed out again, and the chromium more than 98% is left in the slag simultaneously, and the most of vitriol for being adsorbed of the nickel in the leached mud obtains the second solution.Carry out two sections degree of depth dechromisations on the basis of one section preliminary dechromisation, in the mixed solution of the first solution and the second solution, add calcium carbonate, filter, get dechromisation slag and the 3rd solution, adopt sour water washing dechromisation slag to get the 4th solution, two sections dechromisation slags return the leaching operation, and the dechromisation rate can reach more than 91%, and the Ni rate of recovery can reach more than 94%.
5, the recovery of nickel: add calcined soda for industry (Na in the liquid behind the dechromisation
2CO
3) carrying out the enrichment of nickel, the control precipitation temperature is 85 ℃, and the reaction times is 3 h, and endpoint pH is 8.0 to obtain the nickelous carbonate precipitation, by electrodeposition process nickel is reclaimed, and the comprehensive recovery of nickel reaches more than 94%.
Embodiment 4
1, the acidleach of electroplating sludge is processed: electroplating sludge is pumped in the reactor, add sulfuric acid, the pH of stirring reaction system is 4.0, adds hydrogen peroxide according to 20Kg/t mud, and the rear slurry that reacts completely send press filtration to separate, and obtains metal acid leaching solution and body refuse.
2, the heavy copper of sulfuration: leach liquor is heated to 80 ℃, keeping pH is 4.0, directly in stirred reactor, slowly add sodium sulphite, the add-on of sodium sulphite is 1.4 times of chemical mol ratio, reaction 1h, the copper of this moment has been separated with zinc, chromium, nickel, can obtain vulcanizing copper ashes and zinc, chromium, nickel solution through filtering, be further purified and obtain copper sulfide concentrate, the sulfide precipitation rate of copper reaches 97.4%.
3, extracting and separating zinc: add the zinc extraction agent in zinc, chromium, the nickel leach liquor to containing, it is 40% extracting zinc that described zinc extraction agent adopts one or more extraction agents of DPTA, EDTA, phosphoric acid four butyl esters, di-(2-ethylhexyl)phosphoric acid ester to be mixed with by a certain percentage concentration, compare O/A and be defined as 4:1, extraction time is 4min, through the one-level extraction, the percentage extraction of zinc reaches 96.5%.Zinc through the one-level extraction is stayed in the organic phase, with sulfuric acid load organic phases is stripped, and the sulfuric acid concentration of adding is 150g/L, compares O/A=4:1, and shaking does time is 4min, then obtains the high zinc of purity, realizes the separation of zinc.
4, enrichment chromium: carry out one section dechromisation adding calcium carbonate to the solution that vulcanizes after heavy copper and extraction dezincify, the add-on of calcium carbonate is 0.8 times of chemical mol ratio, and the Cr precipitation reaches 97%, and the deposition rate of nickel is 60%, filters, and obtains dechromisation slag and the first solution.With sour water washing dechromisation slag, the nickel in the slag more than 60% is washed out again, and the chromium more than 98% is left in the slag simultaneously, and the most of vitriol for being adsorbed of the nickel in the leached mud obtains the second solution.Carry out two sections degree of depth dechromisations on the basis of one section preliminary dechromisation, in the mixed solution of the first solution and the second solution, add calcium carbonate, filter, get dechromisation slag and the 3rd solution, adopt sour water washing dechromisation slag to get the 4th solution, two sections dechromisation slags return the leaching operation, and the dechromisation rate can reach more than 93%, and the Ni rate of recovery can reach more than 95%.
5, the recovery of nickel: add calcined soda for industry (Na in the liquid behind the dechromisation
2CO
3) carrying out the enrichment of nickel, the control precipitation temperature is 90 ℃, and the reaction times is 3.5 h, and endpoint pH is 7.8 to obtain the nickelous carbonate precipitation, by electrodeposition process nickel is reclaimed, and the comprehensive recovery of nickel reaches more than 94%.
Embodiment 5
1, the acidleach of electroplating sludge is processed: electroplating sludge is pumped in the reactor, add sulfuric acid, the pH of stirring reaction system is 5.0, adds hydrogen peroxide according to 25Kg/t mud, and the rear slurry that reacts completely send press filtration to separate, and obtains metal acid leaching solution and body refuse.
2, the heavy copper of sulfuration: leach liquor is heated to 100 ℃, keeping pH is 5.0, directly in stirred reactor, slowly add sodium sulphite, the add-on of sodium sulphite is 1.5 times of chemical mol ratio, reaction 1h, the copper of this moment has been separated with zinc, chromium, nickel, can obtain vulcanizing copper ashes and zinc, chromium, nickel solution through filtering, be further purified and obtain copper sulfide concentrate, the sulfide precipitation rate of copper reaches 98.1%.
3, extracting and separating zinc: add the zinc extraction agent in zinc, chromium, the nickel leach liquor to containing, it is 50% extracting zinc that described zinc extraction agent adopts one or more extraction agents of DPTA, EDTA, phosphoric acid four butyl esters, di-(2-ethylhexyl)phosphoric acid ester to be mixed with by a certain percentage concentration, compare O/A and be defined as 5:1, extraction time is 4min, through the one-level extraction, the percentage extraction of zinc reaches 97.5%.Zinc through the one-level extraction is stayed in the organic phase, with sulfuric acid load organic phases is stripped, and the sulfuric acid concentration of adding is 130g/L, compares O/A=5:1, and shaking does time is 4min, then obtains the high zinc of purity, realizes the separation of zinc.
4, enrichment chromium: carry out one section dechromisation adding calcium carbonate to the solution that vulcanizes after heavy copper and extraction dezincify, the add-on of calcium carbonate is 1.0 times of chemical mol ratio, and the Cr precipitation reaches 98%, and the deposition rate of nickel is 70%, filters, and obtains dechromisation slag and the first solution.With sour water washing dechromisation slag, the nickel in the slag more than 60% is washed out again, and the chromium more than 98% is left in the slag simultaneously, and the most of vitriol for being adsorbed of the nickel in the leached mud obtains the second solution.Carry out two sections degree of depth dechromisations on the basis of one section preliminary dechromisation, in the mixed solution of the first solution and the second solution, add calcium carbonate, filter, get dechromisation slag and the 3rd solution, adopt sour water washing dechromisation slag to get the 4th solution, two sections dechromisation slags return the leaching operation, and the dechromisation rate can reach more than 99%, and the Ni rate of recovery can reach more than 97%.
5, the recovery of nickel: add calcined soda for industry (Na in the liquid behind the dechromisation
2CO
3) carrying out the enrichment of nickel, the control precipitation temperature is 85 ℃, and the reaction times is 4 h, and endpoint pH is 7.8 to obtain the nickelous carbonate precipitation, by electrodeposition process nickel is reclaimed, and the comprehensive recovery of nickel reaches more than 94%.
The preferred embodiment of the present invention just is used for helping to set forth the present invention.Preferred embodiment does not have all details of detailed descriptionthe, does not limit this invention yet and only is described embodiment.Obviously, according to the content of this specification sheets, can make many modifications and variations.These embodiment are chosen and specifically described to this specification sheets, is in order to explain better principle of the present invention and practical application, thereby the technical field technician can utilize the present invention well under making.The present invention only is subjected to the restriction of claims and four corner and equivalent.
Claims (14)
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103290222A (en) * | 2013-04-08 | 2013-09-11 | 惠州学院 | Method for recovering copper and nickel from electroplating sludge |
| CN104060097A (en) * | 2014-07-04 | 2014-09-24 | 江西省广德环保科技有限公司 | Separating and recycling method of nickel, cobalt, copper manganese and zinc in electroplating sludge |
| CN104745821A (en) * | 2015-02-12 | 2015-07-01 | 江苏恒嘉再生资源有限公司 | Method for recovering nickel and copper metals in acid pickling sludge |
| CN105256141A (en) * | 2015-10-26 | 2016-01-20 | 广西银亿再生资源有限公司 | Electroplating-sludge resourceful treatment and comprehensive recycling method |
| CN105671319A (en) * | 2016-03-25 | 2016-06-15 | 北京天地同源生物科技有限公司 | Mixed electroplating sludge treatment method |
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| CN112010518A (en) * | 2020-09-09 | 2020-12-01 | 佛山经纬纳科环境科技有限公司 | Resource treatment method for sludge containing heavy metals |
| RU2746731C1 (en) * | 2019-12-03 | 2021-04-19 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Челябинский государственный университет" | Method of production of biocide, zinc oxide and magnesium and calcium chloride crystal hydrates from production waste |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB746633A (en) * | 1954-03-11 | 1956-03-14 | Sherritt Gordon Mines Ltd | Improved method of extracting zinc from zinc bearing material |
| EP0262964A2 (en) * | 1986-10-03 | 1988-04-06 | Chevron Research And Technology Company | Recovery of nickel or cobalt from solvent extraction strip solutions |
| CN101063210A (en) * | 2006-04-25 | 2007-10-31 | 襄樊化通化工有限责任公司 | Technique for producing high activity nickel cake with regeneration of waste material containing nickle as raw material |
| CN101195870A (en) * | 2007-12-25 | 2008-06-11 | 金川集团有限公司 | Method for processing waste alloy of nickel cobalt |
| CN101643243A (en) * | 2009-08-14 | 2010-02-10 | 扬州宁达贵金属有限公司 | Method for recovering copper, nickel, chromium, zinc and iron from electroplating sludge |
| CN101648757A (en) * | 2009-09-01 | 2010-02-17 | 浙江大学 | Recycling processing method for stainless steel processing process wastewater grading precipitation |
| CN101871046A (en) * | 2010-06-29 | 2010-10-27 | 青川县天运金属开发有限公司 | Method for recycling heavy metal pollution wastes |
-
2012
- 2012-09-18 CN CN2012103461528A patent/CN102912133A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB746633A (en) * | 1954-03-11 | 1956-03-14 | Sherritt Gordon Mines Ltd | Improved method of extracting zinc from zinc bearing material |
| EP0262964A2 (en) * | 1986-10-03 | 1988-04-06 | Chevron Research And Technology Company | Recovery of nickel or cobalt from solvent extraction strip solutions |
| CN101063210A (en) * | 2006-04-25 | 2007-10-31 | 襄樊化通化工有限责任公司 | Technique for producing high activity nickel cake with regeneration of waste material containing nickle as raw material |
| CN101195870A (en) * | 2007-12-25 | 2008-06-11 | 金川集团有限公司 | Method for processing waste alloy of nickel cobalt |
| CN101643243A (en) * | 2009-08-14 | 2010-02-10 | 扬州宁达贵金属有限公司 | Method for recovering copper, nickel, chromium, zinc and iron from electroplating sludge |
| CN101648757A (en) * | 2009-09-01 | 2010-02-17 | 浙江大学 | Recycling processing method for stainless steel processing process wastewater grading precipitation |
| CN101871046A (en) * | 2010-06-29 | 2010-10-27 | 青川县天运金属开发有限公司 | Method for recycling heavy metal pollution wastes |
Non-Patent Citations (1)
| Title |
|---|
| 郭学益等: "从电镀污泥中回收镍、铜和铬的工艺研究", 《北京科技大学学报》, vol. 33, no. 3, 30 March 2011 (2011-03-30) * |
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| CN104060097A (en) * | 2014-07-04 | 2014-09-24 | 江西省广德环保科技有限公司 | Separating and recycling method of nickel, cobalt, copper manganese and zinc in electroplating sludge |
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| RU2746731C1 (en) * | 2019-12-03 | 2021-04-19 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Челябинский государственный университет" | Method of production of biocide, zinc oxide and magnesium and calcium chloride crystal hydrates from production waste |
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